EP1122806A1 - Solid oxide fuel cell - Google Patents

Solid oxide fuel cell Download PDF

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Publication number
EP1122806A1
EP1122806A1 EP01101352A EP01101352A EP1122806A1 EP 1122806 A1 EP1122806 A1 EP 1122806A1 EP 01101352 A EP01101352 A EP 01101352A EP 01101352 A EP01101352 A EP 01101352A EP 1122806 A1 EP1122806 A1 EP 1122806A1
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EP
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Prior art keywords
fuel cell
solid oxide
oxide fuel
layer
porous
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EP01101352A
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German (de)
French (fr)
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EP1122806B1 (en
Inventor
Niels Christiansen
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Topsoe Fuel Cell AS
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Haldor Topsoe AS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
    • H01M8/0625—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material in a modular combined reactor/fuel cell structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0068—Solid electrolytes inorganic
    • H01M2300/0071—Oxides
    • H01M2300/0074—Ion conductive at high temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to solid oxide fuel cells, and in particular planar solid oxide fuel cells with electrode material supported on a support having integrated in its structure passageways for distribution of cell reactant gases.
  • SOFC solid oxide fuel cells
  • the different fuel cell designs possess a number of advantages and disadvantages such as easy gas manifolding and structural reliability which has been demonstrated for the tubular types, whereas compactness and potential reduction of materials involved are the main advantages of the flat planar design. Very low voltage losses due to low area specific internal resistance can be obtained with the flat planar cell is stacked.
  • the anode-supported thin electrolyte flat plate cell design has some important advantages including low contact resistance between the electrolyte and the anode in addition to simplified and cheaper manufacturing methods based on co-firing of cell components.
  • the anode structure is usually produced by tape casting a mixture of NiO and zirconia powder with a layer thickness of about 0.1 to 1 mm.
  • a thin electrolyte layer is applied for on this anode support layer by spray moulding, dip moulding, layer casting or electrophoretic deposition.
  • the thickness of the thin electrode is typically 10-50 ⁇ m.
  • Reaction rate of electrode reactions is limited by transport of fuel gas and gaseous reaction products through the porous anode structure.
  • the characteristics of the three-phase boundary and the anode porosity therefore take part in the total voltage polarisation of the cell.
  • One solution to this problem is to subdivide the anode into a thin active anode layer with a typical thickness of 1-50 ⁇ m and an anode support and current collecting layer with a typical thickness of 50-1000 ⁇ m, basically consisting of the same mixture of NiO and zirconia.
  • this configuration still fails to fulfil a required effective gas supply through the porous open structure together with a highly mechanically stable support for the electrolyte layer.
  • this invention is an improved SOFC, which integrates the gas supply channels with the cell support and the anode layer. Furthermore, the inventive SOFC makes it possible to produce large cell areas based on cheap manufacturing and materials.
  • FIG. 1 A specific embodiment of a support element of the SOFC according to the invention is shown in Fig. 1.
  • the shown SOFC consists of a porous flat plate 2 containing a number of channels running perpendicular to a cross section of the plate being surrounded on all longitudinal sides by porous walls.
  • the plate's length, width and thickness define the dimension of the flat plate element, where the length is larger than or equal to the width, and the width is larger than or equal to the thickness.
  • the cross section area of the element is defined by the width and the thickness, whereas the planar area is defined by the length and the width.
  • the channels are running parallel to the length of the element.
  • anode layer 8 is deposited as a thin porous layer.
  • the opposite planar side of the porous element is covered by a dense layer 10 .
  • On top of the porous anode layer a thin dense electrolyte layer 12 is deposited.
  • the dense electrolyte layer also covers the rim 14 of the porous elements or solely the rims being parallel with the elongated gas channels.
  • the dense electrolyte covers one of the planar sides, whereas the rim or part of the rim is gas impermeable.
  • the porous element with its longitudinal internal gas channels may be produced by extrusion.
  • the layers deposited on the porous element may be produced by deposition methods like co-extrusion, spray moulding, thermal spraying, dip moulding, printing, casting, laminating, electrophoretic deposition, precipitation deposition, electro-chemical deposition and chemical vapour deposition.
  • the porous element is exposed to reducing gas conditions under fuel cell operation which allows use of material such as ferritic stainless steel, nickel based alloys and high chromium alloys. Based on such metallic materials, the porous element obtains substantially improved mechanical properties and high thermal conductivity ensuring high performance of the fuel cell system, even when large cell dimensions are realised.
  • the thin deposited layers, which penetrate a part of the porous support element become an integrated part of this element and contributes to the high stability and high cell performance. Due to the dimensional stability and rigidity of the porous support element, co-firing of the thin deposited layers is allowed, and larger thermal expansion mismatch between the actual materials is tolerated than in the known cell designs.
  • This cell concept improves the thermal cycling and red-ox stability of the anode and anode current collection layers, since the amount of total nickel content in these layers has been reduced significantly in comparison with known anode-supported SOFC. Furthermore, tight mechanical and physical contact between the different layers may be maintained during thermal cycling and ⁇ red-ox cycling.
  • the dense layer may be based on mixed oxide ceramic materials, which then penetrate into the surface pores of the porous plate element and form an integrated composite interphase structure. Expansion and cracking of these types of ceramic materials, which appear in the traditional thick plate and ceramic bi-polar plates of the known SOFC, are thus eliminated. Furthermore, an effective electrical contact between the anode current collection layer and the cathode current collection layer is established in the mixed ceramic metallic interphase structure.
  • the pores in the porous support element may be impregnated with a catalyst for internal reforming or internal partial oxidation of carbonaceous fuel gasses.
  • Gasses being introduced into the fuel cell electrodes may contain particles contained in the feed gas or from the fuel processing system. It is well known that cell performance degrades over time when particulate impurities are deposited at the electrode surfaces during cell operation.
  • a further advantage of the inventive fuel cell is that the porous plate with its internal gas channels has the function of a particulate trap or filter preventing particulate matter from entering the electrode area, where the electrode reaction takes place.
  • the fuel cell of the invention is therefor particularly useful in operation with feed gases containing dust or other particulate matter.
  • porous support element bonding methods such as soldering and welding can be used to manifold the elements or to connect a number of elements in order to make larger cell structures.
  • planar geometry of the porous support element with its deposited thin anode and electrolyte layer and cathode barrier layer enables this structural element to be repeated, sequentially forming a layered fuel cell stack with minimal internal electrical resistance and maximal structural stability.
  • each porous support plate element is typically in the range from 2 mm to 30 mm, preferably, from 4 mm to 6 mm, the gas channels in the porous support plate elements have cross sectional areas from 0.5 mm 2 to 1000 mm 2 , preferably from 2 mm 2 to 20 mm 2 .
  • the porosity of the porous support plate element is from 20 vol% to 90 vol%, preferably, 30 vol% to 70 vol%.
  • the mean pore size of the porous support plate element is in the range from 0.1 ⁇ m to 500 ⁇ m, preferably, from 1 ⁇ m to 50 ⁇ m.
  • Ferritic stainless steel with powder, the composition Fe22Cr and a mean powder particle size of 100 ⁇ m are mixed in a pug mill with 6 vol% methylcellulose and 44 vol% water followed by extrusion of the paste into a long planar element with the cross-sectional dimension 5x150 mm and with 37 internal longitudinal channels with the cross-sectional dimension 3x3 mm 2 .
  • Each gas channel is surrounded by longitudinal walls with a wall thickness of 1 mm.
  • the thus obtained extruded profiles are cut into lengths of 300 mm in the green stage followed by drying to remove the water content.
  • the dried porous plates are spray-painted on one planar surface with a stabilised slurry consisting of a mixture of NiO powder and zirconia powder doped with 8 mole% yttria in an organic solvent suitable for use in traditional spray painting equipment.
  • the layer is deposited in an even layer thickness of 10 ⁇ m and dried.
  • a further layer consisting of pure fine-grained, well-dispersed suspension of zirconia doped with 8 mole% yttria is then spray-painted on the first layer in an even thickness of 5 ⁇ m.
  • the opposite planar surface of the porous support plate element is spray-painted with a well-dispersed powder suspension containing fine powder of lanthanum chromite doped with strontium and nickel.
  • the layer thickness of this layer is 5 ⁇ m. After drying the spray procedures is repeated one more time.
  • coated element is sintered in hydrogen atmosphere at 1250°C.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

Solid oxide fuel cell with a planar support (2) in form of a porous plate structure supporting on one planar surface a layer of electrode active material (8) and with internally elongated gas supply channels (4) formed inside the structure.

Description

The present invention relates to solid oxide fuel cells, and in particular planar solid oxide fuel cells with electrode material supported on a support having integrated in its structure passageways for distribution of cell reactant gases.
Presently, solid oxide fuel cells (SOFC) are mainly produced in two different designs in form of tubular types and flat planar types. The different fuel cell designs possess a number of advantages and disadvantages such as easy gas manifolding and structural reliability which has been demonstrated for the tubular types, whereas compactness and potential reduction of materials involved are the main advantages of the flat planar design. Very low voltage losses due to low area specific internal resistance can be obtained with the flat planar cell is stacked.
Recent development of thin supported electrolytes for the flat planar cell type in connection with improved electrode performance allows to lower the operation temperature from previously required 1000°C operation temperature, which was typical for self-supported electrolyte cells, to a operation temperature of about 800°C without any reduction in overall cell performance measured as area specific electrical power. Reduction of operation temperature makes it possible to use metallic bi-polar separation plates between the cells. Furthermore, metallic construction materials for the manifolds and heat exchangers leading to improved system reliability and reduced system price can be introduced. Examples of SOFC with thin electrolytes supported by the anode or cathode of the cells are disclosed in the literature (cf. Advances in the Anode Supported Planar SOFC Technology; H.P. Buchkremer et al., Electrochemical Proceedings, Vol. 97-18 (1997); Thin Anode Supported SOFC; S. Primdahl et al., Electrochemical Society Proceedings, Vol. 99-19 (1999); and, Advances in Tubular Solid Oxide Fuel Cell Technology; S.C. Singhal, Electrochemical Society Proceedings, Vol. 95-1 (1995)). Especially, the anode-supported thin electrolyte flat plate cell design has some important advantages including low contact resistance between the electrolyte and the anode in addition to simplified and cheaper manufacturing methods based on co-firing of cell components.
The anode structure is usually produced by tape casting a mixture of NiO and zirconia powder with a layer thickness of about 0.1 to 1 mm. A thin electrolyte layer is applied for on this anode support layer by spray moulding, dip moulding, layer casting or electrophoretic deposition. The thickness of the thin electrode is typically 10-50 µm. During the final firing of the thus obtained multi-layer structure, the anode layer becomes porous with an open porosity in the range of 30-60%, whereas the electrolyte layer densifies to a gas-tight material, while a three-phase boundary (anode-electrolyte-porosity) is established in which the anode electro catalytic reaction takes place. Reaction rate of electrode reactions is limited by transport of fuel gas and gaseous reaction products through the porous anode structure. The characteristics of the three-phase boundary and the anode porosity therefore take part in the total voltage polarisation of the cell. One solution to this problem is to subdivide the anode into a thin active anode layer with a typical thickness of 1-50 µm and an anode support and current collecting layer with a typical thickness of 50-1000 µm, basically consisting of the same mixture of NiO and zirconia. However, this configuration still fails to fulfil a required effective gas supply through the porous open structure together with a highly mechanically stable support for the electrolyte layer. Furthermore, problems with effective mechanical and electrical contact between the porous anode support layer and the bi-polar plates containing the anode gas supply channels still remain to be solved. A number of attempts have been made in the past to improve electrical contact by application of nickel felt in between the anode support layer and the metallic bi-polar plate. Gas supply channels may be formed by machining grooves into the solid metallic bi-polar plate. The above solutions are expensive and not useful in commercial use of SOFC technology.
In general, this invention is an improved SOFC, which integrates the gas supply channels with the cell support and the anode layer. Furthermore, the inventive SOFC makes it possible to produce large cell areas based on cheap manufacturing and materials.
A specific embodiment of a support element of the SOFC according to the invention is shown in Fig. 1. The shown SOFC consists of a porous flat plate 2 containing a number of channels running perpendicular to a cross section of the plate being surrounded on all longitudinal sides by porous walls. The plate's length, width and thickness define the dimension of the flat plate element, where the length is larger than or equal to the width, and the width is larger than or equal to the thickness. The cross section area of the element is defined by the width and the thickness, whereas the planar area is defined by the length and the width. The channels are running parallel to the length of the element. On one of the planar sides of the porous elements, anode layer 8 is deposited as a thin porous layer. The opposite planar side of the porous element is covered by a dense layer 10. On top of the porous anode layer a thin dense electrolyte layer 12 is deposited.
In further an embodiment, the dense electrolyte layer also covers the rim 14 of the porous elements or solely the rims being parallel with the elongated gas channels.
Still in an embodiment, the dense electrolyte covers one of the planar sides, whereas the rim or part of the rim is gas impermeable.
The porous element with its longitudinal internal gas channels may be produced by extrusion. The layers deposited on the porous element may be produced by deposition methods like co-extrusion, spray moulding, thermal spraying, dip moulding, printing, casting, laminating, electrophoretic deposition, precipitation deposition, electro-chemical deposition and chemical vapour deposition.
Containing the fuel gas channels while acting as support for the anode and the dense electrolyte, the porous element is exposed to reducing gas conditions under fuel cell operation which allows use of material such as ferritic stainless steel, nickel based alloys and high chromium alloys. Based on such metallic materials, the porous element obtains substantially improved mechanical properties and high thermal conductivity ensuring high performance of the fuel cell system, even when large cell dimensions are realised. The thin deposited layers, which penetrate a part of the porous support element become an integrated part of this element and contributes to the high stability and high cell performance. Due to the dimensional stability and rigidity of the porous support element, co-firing of the thin deposited layers is allowed, and larger thermal expansion mismatch between the actual materials is tolerated than in the known cell designs. This cell concept improves the thermal cycling and red-ox stability of the anode and anode current collection layers, since the amount of total nickel content in these layers has been reduced significantly in comparison with known anode-supported SOFC. Furthermore, tight mechanical and physical contact between the different layers may be maintained during thermal cycling and ·red-ox cycling.
Interpenetrating of the thin deposited layers on the anode side of the porous support element as well as on the opposite cathode side is decisive for a sufficient electrical and mechanical contact at the interplanes. This is in particular important during thermal cycling of the cell stack and under internal reforming conditions, where large thermomechanical stresses can be tolerated by the porous plate-supported solid oxide fuel cell. The thin dense layer on the cathode side of the porous plate element protects the porous metallic material from oxidation and separates the anode gas from the cathode gas.
The dense layer may be based on mixed oxide ceramic materials, which then penetrate into the surface pores of the porous plate element and form an integrated composite interphase structure. Expansion and cracking of these types of ceramic materials, which appear in the traditional thick plate and ceramic bi-polar plates of the known SOFC, are thus eliminated. Furthermore, an effective electrical contact between the anode current collection layer and the cathode current collection layer is established in the mixed ceramic metallic interphase structure.
The pores in the porous support element may be impregnated with a catalyst for internal reforming or internal partial oxidation of carbonaceous fuel gasses.
Gasses being introduced into the fuel cell electrodes may contain particles contained in the feed gas or from the fuel processing system. It is well known that cell performance degrades over time when particulate impurities are deposited at the electrode surfaces during cell operation.
A further advantage of the inventive fuel cell is that the porous plate with its internal gas channels has the function of a particulate trap or filter preventing particulate matter from entering the electrode area, where the electrode reaction takes place.
The fuel cell of the invention is therefor particularly useful in operation with feed gases containing dust or other particulate matter.
Owing the metallic nature of the porous support element bonding methods such as soldering and welding can be used to manifold the elements or to connect a number of elements in order to make larger cell structures. The planar geometry of the porous support element with its deposited thin anode and electrolyte layer and cathode barrier layer enables this structural element to be repeated, sequentially forming a layered fuel cell stack with minimal internal electrical resistance and maximal structural stability.
The thickness of each porous support plate element is typically in the range from 2 mm to 30 mm, preferably, from 4 mm to 6 mm, the gas channels in the porous support plate elements have cross sectional areas from 0.5 mm2 to 1000 mm2, preferably from 2 mm2 to 20 mm2. The porosity of the porous support plate element is from 20 vol% to 90 vol%, preferably, 30 vol% to 70 vol%. The mean pore size of the porous support plate element is in the range from 0.1 µm to 500 µm, preferably, from 1 µm to 50 µm.
Example 1
Ferritic stainless steel with powder, the composition Fe22Cr and a mean powder particle size of 100 µm are mixed in a pug mill with 6 vol% methylcellulose and 44 vol% water followed by extrusion of the paste into a long planar element with the cross-sectional dimension 5x150 mm and with 37 internal longitudinal channels with the cross-sectional dimension 3x3 mm2. Each gas channel is surrounded by longitudinal walls with a wall thickness of 1 mm. The thus obtained extruded profiles are cut into lengths of 300 mm in the green stage followed by drying to remove the water content.
The dried porous plates are spray-painted on one planar surface with a stabilised slurry consisting of a mixture of NiO powder and zirconia powder doped with 8 mole% yttria in an organic solvent suitable for use in traditional spray painting equipment. The layer is deposited in an even layer thickness of 10 µm and dried. A further layer consisting of pure fine-grained, well-dispersed suspension of zirconia doped with 8 mole% yttria is then spray-painted on the first layer in an even thickness of 5 µm.
The opposite planar surface of the porous support plate element is spray-painted with a well-dispersed powder suspension containing fine powder of lanthanum chromite doped with strontium and nickel. The layer thickness of this layer is 5 µm. After drying the spray procedures is repeated one more time.
Finally, the coated element is sintered in hydrogen atmosphere at 1250°C.

Claims (9)

  1. Solid oxide fuel cell with a planar support in form of a porous plate structure supporting on one planar surface a layer of electrode active material and with internally elongated gas supply channels formed inside the structure.
  2. Solid oxide fuel cell of claim 1, wherein a planar surface on opposite side to the surface supporting electrode active material being provided with a dense layer of gas impermeable and electronic conductive material.
  3. Solid oxide fuel cell of claim 2, wherein the dense layer is a ceramic and/or metallic layer.
  4. Solid oxide fuel cell of claim 1, wherein the electrode layer is active in electrochemical anode reactions and wherein the layer is covered by a further dense layer of electrolyte material.
  5. Solid oxide fuel cell of claim 1, wherein the porous plate is made from ferritic stainless steel, nickel-based alloys and/or high chromium alloys.
  6. Solid oxide fuel cell of claim 1, wherein rim of the porous plate is gas impermeable.
  7. Solid oxide fuel cell of claim 1, wherein rim of the porous plate is supporting a dense layer of electrolyte material.
  8. Solid oxide fuel cell of claim 1, wherein the porous structure is catalytic active in conversion of feed gas to fuel cell reactant gas.
  9. Use of a solid oxide fuel cell according to anyone of the preceding claims in generation of power from particulate matter containing gas.
EP01101352A 2000-02-02 2001-01-22 Solid oxide fuel cell Expired - Lifetime EP1122806B1 (en)

Applications Claiming Priority (2)

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DK200000170 2000-02-02
DK200000170A DK174654B1 (en) 2000-02-02 2000-02-02 Solid oxide fuel cell and its applications

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EP1122806A1 true EP1122806A1 (en) 2001-08-08
EP1122806B1 EP1122806B1 (en) 2012-05-30

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ES (1) ES2385471T3 (en)

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US7842434B2 (en) 2005-06-15 2010-11-30 Ati Properties, Inc. Interconnects for solid oxide fuel cells and ferritic stainless steels adapted for use with solid oxide fuel cells
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JP2008538543A (en) * 2005-04-21 2008-10-30 ザ、リージェンツ、オブ、ザ、ユニバーシティ、オブ、カリフォルニア Precursor material infiltration and coating methods
ES2434442T3 (en) * 2005-08-31 2013-12-16 Technical University Of Denmark Solid reversible stacking of oxide fuel cells and method of preparing it
US7744793B2 (en) 2005-09-06 2010-06-29 Lemaire Alexander B Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom
US7850778B2 (en) * 2005-09-06 2010-12-14 Lemaire Charles A Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom
US9985295B2 (en) * 2005-09-26 2018-05-29 General Electric Company Solid oxide fuel cell structures, and related compositions and processes
JP5498021B2 (en) * 2006-01-09 2014-05-21 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド Fuel cell assembly having porous electrodes
EP2013936A2 (en) * 2006-04-05 2009-01-14 Saint-Gobain Ceramics and Plastics, Inc. A sofc stack having a high temperature bonded ceramic interconnect and method for making same
US20070243451A1 (en) * 2006-04-14 2007-10-18 Chao-Yi Yuh Anode support member and bipolar separator for use in a fuel cell assembly and for preventing poisoning of reforming catalyst
CA2656460A1 (en) 2006-07-28 2008-02-07 The Regents Of The University Of California Joined concentric tubes
ES2394194T3 (en) * 2006-11-23 2013-01-23 Technical University Of Denmark Method for the production of reversible cells of solid oxides
DE102007024225A1 (en) * 2007-05-11 2008-11-13 Deutsches Zentrum für Luft- und Raumfahrt e.V. Support device for an electrochemical functional device, fuel cell module and method for producing a carrier device
US20090166908A1 (en) * 2008-01-02 2009-07-02 Maw-Chwain Lee Innovation control process for specific porosity/gas permeability of electrode layers of SOFC-MEA through combination of sintering and pore former scheme and technology
RU2010147046A (en) 2008-04-18 2012-05-27 Члены Правления Университета Калифорнии (Us) COMBINED SEAL FOR HIGH-TEMPERATURE ELECTROCHEMICAL DEVICE
FR2945378B1 (en) * 2009-05-11 2011-10-14 Commissariat Energie Atomique HIGH TEMPERATURE FUEL CELL CELL WITH INTERNAL HYDROCARBON REFORM.
WO2011062358A2 (en) * 2009-11-23 2011-05-26 주식회사 코미코 Solid oxide fuel cell and method for manufacturing same
JP5362605B2 (en) * 2010-02-05 2013-12-11 日本碍子株式会社 Solid oxide fuel cell
JP2011165379A (en) * 2010-02-05 2011-08-25 Ngk Insulators Ltd Cell of solid oxide fuel cell
US9147890B2 (en) * 2010-05-11 2015-09-29 Ford Global Technologies, Llc Fuel cell with embedded flow field
TWI472090B (en) 2011-04-22 2015-02-01 Univ Nat Cheng Kung Fuel cell solid electrolyte structure
KR20160021872A (en) * 2013-06-29 2016-02-26 생-고뱅 세라믹스 앤드 플라스틱스, 인코포레이티드 Solid oxide fuel cell having a dense barrier layer
US10079393B1 (en) * 2014-01-09 2018-09-18 Bloom Energy Corporation Method of fabricating an interconnect for a fuel cell stack
TWI520425B (en) * 2014-10-30 2016-02-01 行政院原子能委員會核能研究所 A high permeable porous substrate for a solid oxide fuel cell and the production method thereof
KR102518538B1 (en) * 2016-12-16 2023-04-07 현대자동차주식회사 Porous body for fuel cell
CN111837276A (en) * 2018-02-09 2020-10-27 日产自动车株式会社 Method for activating anode layer in solid oxide fuel cell, and solid oxide fuel cell system
CN112993267A (en) * 2019-12-18 2021-06-18 中国科学院宁波材料技术与工程研究所 Direct methane dry reforming power generation method based on solid oxide fuel cell with symmetrical double-cathode structure

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH515622A (en) * 1969-10-22 1971-11-15 Raffinage Cie Francaise High-temp solid electrolyte fuel cell - with composite electrode/elec
EP0414270A2 (en) * 1989-08-24 1991-02-27 Kabushiki Kaisha Meidensha Fuel cell utilizing solidous electrolyte
JPH0355764A (en) * 1989-07-21 1991-03-11 Fuji Electric Co Ltd Solid electrolytic type fuel cell
JPH03283266A (en) 1990-03-29 1991-12-13 Nkk Corp Solid electrolyte fuel cell of inside reformed type
JPH0837011A (en) 1994-07-25 1996-02-06 Nippon Telegr & Teleph Corp <Ntt> Hollow flat fuel cell substrate
US5589286A (en) 1993-07-21 1996-12-31 Fuji Electric Co., Ltd. Solid electrolyte fuel cell
WO1997023007A2 (en) 1995-12-20 1997-06-26 Forschungszentrum Jülich GmbH Electrode substrate for fuel cell
EP0785587A2 (en) 1996-01-18 1997-07-23 Ngk Insulators, Ltd. Layered sintered body for electrochemical cell, electrochemical cell including it and process for its manufacture
EP0788175A1 (en) * 1996-02-02 1997-08-06 Sulzer Innotec Ag High temperature fuel cell with an electrolyte thin film
WO1998035398A1 (en) * 1997-02-11 1998-08-13 Bossel Ulf G Fuel cell stack with solid electrolytes and their arrangement

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61253772A (en) * 1985-05-02 1986-11-11 Hitachi Ltd Method for cleaning fuel-reforming device
JP2724617B2 (en) * 1988-07-07 1998-03-09 東海カーボン株式会社 Porous metal material
JP2531824B2 (en) * 1990-03-27 1996-09-04 日本碍子株式会社 Solid oxide fuel cell
JP2528986B2 (en) * 1990-02-15 1996-08-28 日本碍子株式会社 Solid oxide fuel cell
JPH04160760A (en) * 1990-10-22 1992-06-04 Yuasa Corp Inside reforming type fuel cell
JPH04280074A (en) * 1991-03-08 1992-10-06 Nippon Telegr & Teleph Corp <Ntt> Solid electrolyte fuel cell
JP3057342B2 (en) * 1992-07-09 2000-06-26 工業技術院長 Solid electrolyte fuel cell
JPH06338336A (en) * 1993-05-31 1994-12-06 Nippon Telegr & Teleph Corp <Ntt> Conductive non-uniform hollow flat plate
JP3166888B2 (en) * 1993-09-21 2001-05-14 日本電信電話株式会社 Solid oxide fuel cell stack
GB9403198D0 (en) * 1994-02-19 1994-04-13 Rolls Royce Plc A solid oxide fuel cell stack
US5460897A (en) * 1994-03-18 1995-10-24 Allied Signal Inc. Solid oxide fuel cell stacking assembly
JPH08138690A (en) * 1994-11-07 1996-05-31 Tonen Corp Solid oxide fuel cell
ATE191992T1 (en) * 1995-01-16 2000-05-15 Sulzer Hexis Ag ELECTROCHEMICALLY ACTIVE ELEMENT FOR A PLANAR HIGH TEMPERATURE FUEL CELL
DE19519847C1 (en) * 1995-05-31 1997-01-23 Forschungszentrum Juelich Gmbh Anode substrate for a high temperature fuel cell
DE69601838T2 (en) * 1995-07-28 1999-10-14 Nippon Telegraph And Telephone Corp. Fuel cell with solid oxide electrolytes
JP3137177B2 (en) * 1995-07-28 2001-02-19 日本電信電話株式会社 Solid oxide fuel cell
US6228520B1 (en) * 1997-04-10 2001-05-08 The Dow Chemical Company Consinterable ceramic interconnect for solid oxide fuel cells

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH515622A (en) * 1969-10-22 1971-11-15 Raffinage Cie Francaise High-temp solid electrolyte fuel cell - with composite electrode/elec
JPH0355764A (en) * 1989-07-21 1991-03-11 Fuji Electric Co Ltd Solid electrolytic type fuel cell
EP0414270A2 (en) * 1989-08-24 1991-02-27 Kabushiki Kaisha Meidensha Fuel cell utilizing solidous electrolyte
JPH03283266A (en) 1990-03-29 1991-12-13 Nkk Corp Solid electrolyte fuel cell of inside reformed type
US5589286A (en) 1993-07-21 1996-12-31 Fuji Electric Co., Ltd. Solid electrolyte fuel cell
JPH0837011A (en) 1994-07-25 1996-02-06 Nippon Telegr & Teleph Corp <Ntt> Hollow flat fuel cell substrate
WO1997023007A2 (en) 1995-12-20 1997-06-26 Forschungszentrum Jülich GmbH Electrode substrate for fuel cell
EP0785587A2 (en) 1996-01-18 1997-07-23 Ngk Insulators, Ltd. Layered sintered body for electrochemical cell, electrochemical cell including it and process for its manufacture
EP0788175A1 (en) * 1996-02-02 1997-08-06 Sulzer Innotec Ag High temperature fuel cell with an electrolyte thin film
WO1998035398A1 (en) * 1997-02-11 1998-08-13 Bossel Ulf G Fuel cell stack with solid electrolytes and their arrangement

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
DOKIYA M ET AL: "WET PROCESS FOR PLANAR SOFC", PROCEEDINGS OF THE INTERNATIONAL SYMPOSIUM ON SOLID OXIDE FUEL CELLS,LU,LUXEMBURG, EEC, vol. SYMP. 2, 2 July 1991 (1991-07-02), pages 127 - 134, XP000546102, ISBN: 92-826-2556-7 *
PATENT ABSTRACTS OF JAPAN vol. 015, no. 204 (E - 1071) 24 May 1991 (1991-05-24) *
PATENT ABSTRACTS OF JAPAN vol. 016, no. 104 (E - 1178) 13 March 1992 (1992-03-13) *
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 06 28 June 1996 (1996-06-28) *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1306920A3 (en) * 2001-10-24 2006-09-06 Nissan Motor Co., Ltd. Unit cell for fuel cell and solid oxide fuel cell
WO2006010260A1 (en) * 2004-07-27 2006-02-02 Versa Power Systems, Ltd. Anode supported solid oxide fuel cell with a porous multifunctional layer
US8287673B2 (en) 2004-11-30 2012-10-16 The Regents Of The University Of California Joining of dissimilar materials
WO2009014775A2 (en) 2007-07-25 2009-01-29 The Regents Of The University Of California High temperature electrochemical device with interlocking structure
EP2210307A4 (en) * 2007-07-25 2011-09-28 Univ California ELECTROCHEMICAL HIGH TEMPERATURE DEVICE WITH LOCKING STRUCTURE
EP2031684B1 (en) * 2007-08-31 2016-08-10 Technical University of Denmark Metal supported solid oxide fuel cell
EP2045861A1 (en) 2007-10-05 2009-04-08 Topsøe Fuel Cell A/S Seal for porous metal support in a fuel cell
US8227131B2 (en) 2007-10-05 2012-07-24 Topsoe Fuel Cell A/S Seal for a fuel cell support
US8409759B2 (en) 2007-10-05 2013-04-02 Topsoe Fuel Cell A/S Seal for a fuel cell support
EP2273595A1 (en) * 2009-06-30 2011-01-12 NGK Insulators, Ltd. Solid oxide fuel cell
AT15927U1 (en) * 2017-03-16 2018-09-15 Plansee Se Functionalized, porous gas guide part for electrochemical module

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US6783880B2 (en) 2004-08-31

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